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Corrosive Joeseph
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https://www.sciencemadness.org/whisper/viewthread.php?tid=20...
/CJ
[Edited on 27-2-2019 by Corrosive Joeseph]
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Tsjerk
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Nice review CJ!
This one does work wonderfully on β-Nitrostyrenes though. In methanol/aqueous HCl at least.
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strychnineissweet
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Quote: Originally posted by Chemi Pharma  | | Quote: Originally posted by strychnineissweet | I'm not sure what you mean by how is it dehydrated.....the dehydration isn't solvent dependent. The majority of your reaction mixture will solidify,
but only upon final cooling. You will be left with some orange-red liquid, but the lions share will solidify. This is the best yielding reaction
method that I personally have found.
I don't have any thoughts as to Urushibara Nickel, but I can say that the NaBH4 + NiCl2 doesn't work. I lost many hours and lots of starting material
trying to get it to - don't waste your time with that one. Your best bet really honestly is using Hg/Al. You can deal with the waste Hg by treating
it with sulfur and turning it into cinnabar - a naturally occurring ore. Hg/Al is also going to be your best yielding, just shy of LAH.
Also, do future-you a favor and save a seed crystal of your nitropropene to help your future reactions crystallize. That is beyond all other methods
the best and easiest way to induce crystallization.
Your product is most certainly P2NP, you should be happy with those crystals - they look good. I always used IPA to recrystallize, but I don't see
why MeOH wouldn't work just as well. Any other questions I can answer please ask - I love helping other chemists work through places I've been
before! |
I Agree with almost everything you wrote. You seems have a lot of experience in this process. I did many and many experiences in this way years ago in
the University lab, just with scientific purposes of course, just to know if I was able to produce amphetamine salts.
At those times the studies with borohydrides and transition metal couples were at the beggining and was hard to find reliable references and
experimental sections inside the researchs I barely get found at the web.
However I got found some articles talking about nickel boride and it's reductive power. I have experimented the P2NP reduction with NABH4 and NICl2
the same way the recipe I brought attached in my last comment and I got amphetamine. The smell of the amine is unmistakable but the yield sucks and I
had some troubles with the work up.
First of all, every time I stripped of the methanol and add an acid, I got a red dark resin that ruins down all the reaction. Cause this I change the
method from A-->B-->A to B-->A-->B. Researching a lot I discovered this dark red resin is some kind of nickel organic complex. Other thing
to know it's not to use HCl in the work up followed or by Dicloromethane, cause amphetamine chloridrate is somewhat soluble in DCM. Use dilute
sulfuric acid and work with the amphetamine sulphate.
I want to know from you about your negative experience reducing P2NP with NABH4 and NiCl2. Could we change some words about this? I'm quite interested
in your personal experience.
| Quote: Originally posted by karlos³ | | Use NaBH4/CuCl2, it happens to become the new standard among a group of clandestine chemists, putting the Al/Hg to rest for now.
|
Karlos, could you give me more information about this method using copper boride instead nickel boride? I have read an article I donloaded here in the
Forum talking about substituted nitrostyrene reduction to dopamine, but it's too much generical. Do you have any papers talking about NABH4/CuCl2 or
CUSO4? I'm very interested on it. |
My experience with the NaBH4/NiCl2 is that it destroyed everything, and as a result I was unable to recover any product OR any nitropropene. I'll be
the first to admit that I have no idea where it went, because it sure didn't bubble out as CO2. I attempted this reaction several times, and had the
same result each time.
I also attempted Zn/HCl reduction, which if I recall correctly only reduces the nitropropene to a nitropropane, not the amine. This reaction was quite
vigorous, but ultimately didn't produce any amine product for me. The only reduction condition that I have ever had success, and very high yielding
success with is with Al/Hg. I was getting >90% yield every time, and the workup and purification was just so simple and straightforward that I
never put much stock in other methods beyond the ones that I tried. Most of my true experimentation was with the nitropropene synthesis, as I has such
good luck with the reduction to amine right away that it never really warranted much prodding.
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Chemi Pharma
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Here's an article I just have found about NaBH4/CuSO4 couple reductions:
Attachment: Reduction Of Aliphatic Nitro Compounds To Amines Using NaBH4_CuSO4.PDF (132kB)
This file has been downloaded 828 times
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karlos³
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| Quote: Originally posted by Chemi Pharma |
Karlos, could you give me more information about this method using copper boride instead nickel boride? I have read an article I donloaded here in the
Forum talking about substituted nitrostyrene reduction to dopamine, but it's too much generical. Do you have any papers talking about NABH4/CuCl2 or
CUSO4? I'm very interested on it. |
Yes of course, but it is not copper boride which act as the reducing agent there, just the copper nanoparticles are what is doing the job here.
Take a look here: http://www.sciencemadness.org/talk/viewthread.php?tid=84596
Joe(also my favorite librarian  ) is wrong with this claim but he couldn't know
it.
Well, still partially right, since while this reduction was adapted by the clandestine community with some changes, there really is a reference
existing.
The changes made are practical, a bit less of borohydride(6x at least), and, logically also a different workup depending on the product is done, which
makes that route even more convienient, easier to carry out, with less work involved too.
It could be that it is somewhat based on the NaBH4/CuSO4 paper out there, but I don't know it for sure.
The differences I am talking about are in detail, 6 instead of 7,5 equivalents of borohydride, usually.
For valuable substrates, I would still use up to 7,5 molar equivalents of borohydride, as that will be in almost any case be the cheaper reagent here.
In case an amine able to get steam distilled is the product, then we do this different workup instead: acidic quench with aq. acetic acid after the
reaction, distill the alcoholic solvent off, freebase it and steam distill the product off.
In case the amine is not, like a subst. phenethylamine, we still distill the alcoholic solvent off, and then after basification, extract the amine
with portions of for example DCM, from which the product is recovered by the usual means.
Do not, I repeat, do not use the workup method cited in the paper!
They do it this crude only because they purify their result only later on sufficiently enough.
| Quote: Originally posted by Chemi Pharma | Thank you @/CJ, you are my favorite librarian and historian here on this Forum!
| Quote: Originally posted by Corrosive Joeseph | | followed by reductive amination with zinc, nickel acetate and aqueous NH3 has finally been proven, hitting a whopping 84% with the last one. Based on
Scr0t's cyclohexylamine synthesis. Also found here. |
@/CJ, where's the reference? I think you forgot to add the link, I guess!
[Edited on 27-2-2019 by Chemi Pharma] |
Comes from patent FR 971429 from the 40ies.
Barely noticed while a very valuable gem, we have in that paper not only reductive aminations, but reductions of some other very interesting
substrates.
Like, Nitrosoketones to amino alcohols, double bonds, oximes, ketones, nitriles and lastly, nitro groups too... and all in high yields.
(no, it can not yet reduce nitroalkenes, does not work under the conditions this bimetallic reagent system is used in...)
I can really vouch for his claim, the 84%, that was really neat in every aspect!
It also was the substrate doing best in that synthesis for the chemist in question, at least among that half dozen of different starting materials he
tried(reducing different functional groups mostly, not only aminating ketones).
The same substrate in a second experiment yielded still above seventy percent, due to being carried out using less vigorous conditions with reduced
reagent quantities(to the theoretical needed amount, but on a really small scale), and was just done as concept of proof.
When doing it exactly like Scr0t's second experiment, one can possibly aminate whatever ketone one wants to with good yield, as his second experiment
is optimised, it runs much better and smoother this way.
(Joe, you are an awful person! Making a grown man blush like a little girl! 
 )
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nimgoldman
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Thanks for all the input and references!
I know Al/Hg works, but I am quite opposed to working with highly toxic materials. My original project is actually getting to amphetamine all the way
from bitter almond kernels (or bitter apricot kernels) using only easy to obtain materials. This is just a hobby project.
The reason for choosing Urushibara nickel was 1) the fact I found some tricks to improve it's activity based on NurdRage and ChemPlayer's videos, 2)
that I have NiCl on hand, which is readily available, unlike HgCl which I was unable to get without causing unwanted attention, 3) becasue I read in
some chemistry texts, that aliphatic nitro groups can be reduced to amino groups using zinc and acetic acid ... but I might not work after all and I
have to get back to the drawing board and books (still having lot to learn unfortunately).
What seems more plausible now is making the ketone (phenylacetone) followed by the Leuckart reaction.
In the worst case, I was thinking about making water soluble Hg salt from cinnabar (which is easily obtained), but this would spawn another huge
project.
Even getting to phenyl-2-nitropropene took several months of preparations (mostly going through hardships of making nitroethane and almost every
non-working method there is), it seems one step away from finishing the project, but maybe the hardest part is actually there.
[Edited on 28-2-2019 by nimgoldman]
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Corrosive Joeseph
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Followed by..........
| Quote: Originally posted by Tsjerk | Nice review CJ!
This one does work wonderfully on β-Nitrostyrenes though. In methanol/aqueous HCl at least.
|
Thank you, Tsjerk.
Yes, it works well with beta-substituted hydrogens, but seemingly not so good with beta-substituted methyl groups........ Which confusingly (for some
people, at least), become the alpha substituents upon reduction.
Of course, the atoms don't move, this is just the nomenclature, because styrene carbons are counted from the phenyl ring (because they are styrenes),
and amine carbons are counted from the amino group, obviously........ because they are amines.
The zinc and HCl reduction of phenylnitrostyrenes, especially phenylnitropropenes has never been properly explored in my opinion.
Characterization has always been poor and if people don't hit the active amine, many seem to call failure, and this has been repeated on the boards ad
nauseum. Nobody seems to want to poke about in that slop.
Molecules with ring methoxys and substituents seem to do well, and the original researchers hit the oximes a number of times in ~50% and 'good
yields', respectively.
2,3-dimethoxynitrostyrene - https://sci-hub.se/10.1007/BF00899898
1-anisyl-2-nitropropene and 2-nitro-l-piperonylpropene - https://chemistry.mdma.ch/hiveboard/rhodium/pdf/pseudonitros...
In my link quoted by Tsjerk, GC_MS reports a yield of 80:20, ketone:amine, on 4-methoxyphenyl-2-nitropropene, probably using GC-MS analytical
equiptment............ One would hope, with a username like that.
Another good review can bee found here.
''Selective Reduction of Conjugated NitroOlefins'
https://etd.ohiolink.edu/!etd.send_file?accession=osu1448465...
Keeping the reaction cold and having a high dilution (and the correct amount of acid) seems to help avoid the hydrolysis......... And there is also
this.
"Nitroethenes and nitropropenes are electronically analogous to alpha,beta-unsaturated ketones(the classical Michael acceptor). The benzyllic carbon
is electrophillic and is subject to attack by suitable nucleophiles, which in the case of nitrostyrene reductions could either be the fully reduced
amine or the deprotonated nitroethane(electronically analogous to an enolate). Both nitroethenes and nitropropenes are good michael acceptors, and a
deprotonated nitroethane is a good nucleophile, but a deprotonated nitropropane is usually so sterically hindered that it is not very reactive as a
nucleophile, and dimerization is therefore much less of a problem in nitropropene reductions than it is in nitroethene reductions."
And as we all know, addition in a dissolving metal reduction happens in a 1,2 fashion, and not in a 1,4.
Analogous to an electro-chemical reduction.......... 
This means the nitro group is attacked preferably over the double bond, and reduction should happen 'from that end'.
The oxime of 1-phenyl-2-propanone has also been reduced to the amine in 76%, again using zinc, nickel(II)acetate and aqueous ammonia.
Another tried this system with the beta-methyl nitrostyrene and reported failure,
[EDIT] - No amine
but only one test was done, and it is possible his homemade Ni(II)acetate and low quantity of zinc contributed to this. Possibly something as simple
as more acidic conditons are needed. Although, nitropropenes are much less prone to dimerization under basic conditions than nitrostyrenes.
But I do believe something else which is unproven at this point in time...........
So after all that, it would appear that iron, nickel(II)acetate, acetic acid and H20 should work even better to reduce the beta-methyl nitrostyrene to
the saturated amino compound.
Because for nearly 100 years now, it has been known that addition of a nickel salt to an iron and acid reduction will cause the reaction to go to
completion and to occur in less time. 2 hours instead of 8
http://www.orgsyn.org/demo.aspx?prep=CV1P0304
And exactly as has been shown to work with another a,b unsaturated compound, cinnamaldehyde............. In 1924
https://sci-hub.tw/10.1021/ja01675a014
They also noted in that paper, that the zinc reduction of the unsaturated compound produced a mix of products, and that iron and mildly acidic
conditions gave good results,
keeping the double bond, which is the case of beta-methyl-nitrostyrene, amazingly quite similar, except the double bond seems to 'crack open and swing
around, forming the unsaturated oxime. So, not surprising really, that both compounds do this.
And iron is less reactive than zinc.
/CJ
[Edited on 28-2-2019 by Corrosive Joeseph]
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nimgoldman
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Thanks for all the sources and articles. I have skimmed some of them and will try some of the approaches, then post the results in appropriate thread.
The community is really helpful!
Fortunately, I have plenty of NaBH4 to experiment with so I can try using it either with NiCl or CuSO4 as advised. I might try the freshly prepared
and activated Urushibara type-A catalyst for fun if I will have some phenyl-2-nitropropene (now beautifully recrystallized) left over.
Of course, the reduction has been done a billion plus one times in both pharmaceutical industry and clandestine laboratories, so I believe such
reduction is a fairly well tried and tested process. It amazes me there is still a discussion actually, and so little well-written writeups.
The scientific literature I have calls either for LAH in THF or the Leuckart reaction, which I think is harder to work up as there are more organic
impurities and side products.
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Corrosive Joeseph
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You are very welcome.
Notice that certain members are very interested in this, well, there is a reason for that.
The reduction of this conjugated nitro compound in one step has tortured chemists for over a century now. There is so little discussion because it is
so difficult.
Some of the routes I have posted have only been developed in the last year or two. This is why there are not really any write-ups.
I don't know what Big Pharma do, surely hydrogenation and more than likely not in one step from P2NP.
The mafias of Europe have been using the low-yielding Leuckart for about 40 or 50 years in a 'hand-me down' recipe. Same again, the nitropropene has
to bee taken to the ketone first.
There is so much disconnect between them and the community that nobody here (or anywhere) really knows a decent Leuckart procedure, and so far
the best Leuckart I have personally seen was 48%
And that was reported by another experimenter 6 weeks ago, not here. Before that, user 'logical' reported a yield in the 60's, but that was over two
decades ago on the old Hive board.
Nothing much of note in between then.
The Al-Hg has been the gold standard in the community for about 20 years, when it was reported by Antoncho and those
tenacious bees over at the HyperLab, and was based on earlier pioneering work of Sunlight who discovered it would work on reducing
2,5-dimethoxynitrostyrene.
And nobody wants to use it.
The only major discovery since then was the work of stoichiometric_steve, posted here -
general high-yielding one-pot procedure for the reduction of conjugated aliphatic nitro groups - https://www.sciencemadness.org/whisper/viewthread.php?tid=49...
Based on the work of Bandil and Barium, https://chemistry.mdma.ch/hiveboard/methods/000460139.html
but you must NEVER believe a word posted by Barium, almost everything he wrote was utter fiction and many have wasted their chemicals following his
write-ups and bullshit.
There are a couple of NaBH4 reduction write-ups, and reducion of the nitropropane can bee done with zinc or iron and most acids.
LAH is dangerous, explosive and hard to obtain, and apart from Alexander Shulgin and one scientific paper (Gilsdorf and Nord 1952),
you will not find much on that one either.
Apologies, maybe I dumped too much information on you in one go, but from what I read, NaBH4/NiCl2 and NaBH4/CuSO4 will not work, or at least, not
very well or consistently.
'NaBH4/CuSO4 nitro reduction success!!' - https://sciencemadness.org/talk/viewthread.php?tid=6733
'new/old nitroalkene reduction method' - https://sciencemadness.org/talk/viewthread.php?tid=7190
'New nitroalkene reduction with NaBH4 / Cu(OAc)2' - https://chemistry.mdma.ch/hiveboard/novel/000246001.html
This is why this reduction is such an academic pursuit. It really is a genuine and legitimate scientific puzzle. Up until fairly recently, every route
has what people regard as one major drawback or another.
/CJ
[Edited on 1-3-2019 by Corrosive Joeseph]
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Chemi Pharma
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@/CJ I enjoyed your explanations, references and historical data about the one pot reduction of P2NP to amphetamine. I understand now there are too
much controversy! I read all the references you've posted and I want to know from you if the reference I quoted, from "Cabbage family" worth a try? is
it reliable?
And just for curiosity. Why did you write "(yes, I know)" in parenthesis while writing about this reference?
As a note, reading all the thread you've posted, signed by @Stoichiometric_Steve, now I'm felling relieved, cause now I know the problem in not me.
This guy is really rude with a lot of other members here, since 2006, as we can see reading the humiliation he tryed to do against @pharmacological.
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karlos³
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nimgoldman, don't use CuSO4, that sulfate is an inferior salt.
Better use the chloride, that is for some reason others can explain better almost functioning ideally(only the bromide, acetate, likewise maybe, are
better to use here).
As for the nickel salts, I did the reduction of an oxime(l-phenacetylcarbinol) maybe 3-4 times already with the hydrates of both NiCl2(just once) and
Ni(II)acetate(the remaining few times).
Yield was always improvable, but rather bad only that one time when I fumbled some reduction together myself(MeOH/DCM solvent combination), and got
around ~28%, with the reduction being enriched with a little bit of the PTC agent triethylbenzylammonium chloride(0,25eq. mol of that PTC agent for
one mol of borohydride).
On nitrostyrenes/-propenes Joe is right, it won't work satisfying if at all, I am sure.
Nothing else for LiAlH4 for the reduction of nitropropenes?
I think our member Halogen did it on simple P2NP with an acceptable yield, no?
@Chemi Pharma:
That is just the way stoichiometric_steve is...
If you find him already offensive, you would have had a hard time at the old hive I have to say
So better to just look over it, and if it offends you this much, then just shrug it off.
Because after all, he posts contain really worthwhile experimental data, with his findings being composed of very valuable details.
[Edited on 28-2-2019 by karlos³]
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zed
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Assuming that a procedure for the reduction of a nitrostyrene, will work to reduce a nitropropenylbenzene, is just wrong thinking. Logical
thinking.... perhaps even clever thinking, but wrong thinking.
Generally, the first stage of a nitrostyrene reduction, produces an aldoxime. This aldoxime, is then further reduced, to an amine.
The first stage of reduction, of a nitropropenylbenzene, produces a ketoxime. Regretfully, those ketoximes are quite resistant to further reduction.
Furthermore, during most types of nitrostyrene or nitropropenylbenzene reductions, acetic conditions are probably preferable.
Otherwise, extensive polymerization may occur.
Thus the dark crud, instead of a usable product.
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clearly_not_atara
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CuSO4 is much less soluble in organic solvents than CuCl2. I assume the copper particles are much smaller when using CuCl2 than CuSO4, with Cu(OAc)2
somewhere in between. Following this trend CuBr2 may be even better since it is more covalent, but more expensive. (the correlation is more covalent
-> more soluble -> better catalyst)
CuCl2 seems to work fine. I assume that you can convert the sulfate to the chloride with CaCl2 which is widely available as an air dehydrator
(DampRid) or road deicer.
[Edited on 04-20-1969 by clearly_not_atara]
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Corrosive Joeseph
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| Quote: Originally posted by Chemi Pharma | if the reference I quoted, from "Cabbage family" worth a try? is it reliable?
And just for curiosity. Why did you write "(yes, I know)" in parenthesis while writing about this reference?
|
Is it reliable...........? I don't know.......... I would hope so, but my wishful thinking does not work on the same laws as chemistry.
If you look through the whole paper, you will read stuff like this
| Quote: Originally posted by Chemi Pharma |
Example 5.2 Psychotria douarrei Plant
Calcining: The calcining is carried out according to the standard programme (300° C. for 2 hours, then 550° C. for 3 hours).
Preparation of the catalyst: 1 g of Psychotria douarrei ash is taken. A minimum of 12N HCl is added to the ash (approximately 20 mL); all of the solid
passes into solution and rapidly becomes a pale green colour. After 2 hours at 60° C., the mixture is evaporated at 80° C., filtered and produces 1
g of a fine powder having a pale yellow colour, the colour of dehydrated nickel dichloride.
Results of ICP-MS (Table XIV):
TABLE XIV
Mg Al Ca Fe Cu Zn Cd Pb Mn Ni
Ash 87020 880 105945 260 4740 7040 20 300 260 185600
Crude catalyst 78240 1620 93719 1760 4560 5760 14 360 1160 270320
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The patent is VERY long and has loads of other 'madness' in there about 'doped' nickel catalysts made from plants fed on huge amounts of metals.
(yes, I know)
Now do you get why I said that............?
And that's just TOO weird............. But I think I get what's happening here now. All the trace metals and minerals are exchanging charge, bouncing
it about while it changes each time.
This actually reminds me of Organikum's (by now) famous post about metal impurities.
'Some remarks regarding older chemistry texts' - https://chemistry.mdma.ch/hiveboard/newbee/000478009.html
I don't know why, but the first thing that comes to mind is precipitation of Ni(0) from nickel chloride with zinc followed by addition of aluminum
grains will do a similar thing. (Tri-metallic couple!)
But maybe it will work with regular NiCl2 and aluminum grains (and NOT the aluminum foil used by Ritter)............ Who knows.
Another thing to note is that in the procedure, the HCl acid is added in increments, leading me to think this helps with the reduction, reducing 'a
little bit at a time', keeping the mix slightly acidic, but never too much, because if it was all added at once, the phenyl-2-nitropropene would just
hydrolyse on it's way to the amine. That's the thinking anyways.
/CJ
[Edited on 1-3-2019 by Corrosive Joeseph]
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karlos³
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Thank you for the explaination about the different salts affecting the microparticle size(and thus the ability of the reduction going to completion).
Considering how little of the copper salt is actually used here, it may be very valuable to switch to using CuBr2 for the reduction instead...
May have to try that soon, it is after all either cheap to acquire or easily and simply made if one has some HBr readily one hand.
| Quote: Originally posted by clearly_not_atara |
CuCl2 seems to work fine. I assume that you can convert the sulfate to the chloride with CaCl2 which is widely available as an air dehydrator
(DampRid) or road deicer. |
I had once, because I lacked the patience to wait on it getting delivered, prepared some CuCl2 out of hardware store copper tubing(HNO3 and H2SO4 to
the sulfate), then worked via that to the chloride(no OTC CuSO4 here to be found or maybe I have lost all the skills once had in discovering OTC
chemicals, so had to reside to this).
I found it very straight forward to convert the obtained CuSO4 solution to the carbonate directly, then react the filtered copper carbonate with HCl.
All in all from buying the tubing and having the CuCl2 ready took me only a half day if my memory serves me right.
But it may be easier when one already has a container of pure CuSO4 already on hand to do it with calcium chloride.
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Chemi Pharma
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Nurd Rage teaches in his you tube video how to produce CuCl2 in three ways. One of this is from CuSO4. See here: https://www.youtube.com/watch?v=V8mHiFYmlBc
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nimgoldman
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| Quote: Originally posted by Corrosive Joeseph | | Apologies, maybe I dumped too much information on you in one go, but from what I read, NaBH4/NiCl2 and NaBH4/CuSO4 will not work, or at least, not
very well or consistently.[Edited on 1-3-2019 by Corrosive Joeseph] |
I just tried the NaBH4/NiCl2 procedure that Chemi Pharma proposed few posts back, but it didn't worked.
I followed the procedure to the letter and everything worked perfectly, even the smell of amine was very distinctive and I already though I have the
desired propanamine. Well, I didn't.
The product simply refused to precipitate. I tried pulling it in dry acetone, then crash it out with conc. sulfuric acid - no result. Then I tried HCl
- no result. I tried pulling it in IPA and add sulfuric - no result. I tried adding hexane to lower solubility but it only pushed everying into
separate aqueous layer.
I was desperate and even tried IPA + ether which produced some clouding that quickly disappeared. I managed to make white precipitate in one test
tube, but that ether was impure and I had to distill it first.
Meanwhile I placed the product in the freezer and when I finally had my ether, I pulled the product in IPA and added ether... and no reaction again.
So I ended up kind of frustrated and maybe some day try the Leuckart reaction. I came all this way to the nitropropene only to realize the damn super
toxic mercury seems to be the only way... well I don't want to use mercury since I am a home experimenter and not skilled in handling highly toxic
substances unfortunately. I just wanted to make a writeup on making an interesting psychoactive compound on microscale using only easily available and
as eco-friendly materials as possible...
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nimgoldman
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Okay I've read the following paper from 1994 suggesting several routes from phenyl-2-nitropropene to phenyl-2-aminopropane (amphetamine):
| Quote: | | DeRuiter, Jack, C. Randall Clark, and F. Taylor Noggle. "Gas chromatographic and mass spectral analysis of amphetamine products synthesized from
1-phenyl-2-nitropropene." Journal of chromatographic science 32.11 (1994): 511-519. |
One method requires Pd/C catalyst and hydrogenation in a Parr apparatus, neither of which I have.
Another method uses LAH in THF, which is known to work but even though I can get both LAH and THF, the procedure requires dry THF and many precautions
as there are fire and explosion hazards.
Finally two other methods work on phenyl-2-pronanone and look much more viable (the synthesis of the phenyl-2-pronanone intermetidate is included in
the paper):
One method uses sodium cyanoborohydride and ammonium acetate in methanol, which I am able to perform. I still hesitate in using the precious
cyanoborohydride as I save it for another reactions.
Second method uses the Leuckart amination (using formamide). The researchers didn't use a Kugelrorh for workup and the GC-MS spectra still looked very
good.
I will post this in a new, more relevant thread, summarizing what others posted to the topic since all this went OT.
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Corrosive Joeseph
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Will you do me a favour and keep it here please. In my opinion, you have two real options.........
(1) Iron and acid to the ketone, steam it out, vacuum distill, zinc-nickel-NH3 to the primary amine.
(2) NaBH4-CuCl2 one-pot
You can thank me later.
/CJ
Attachment: deruiter1994.pdf (1.5MB)
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Being well adjusted to a sick society is no measure of one's mental health
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karlos³
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Mood: oxazolidinic 8)
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I agree very much on that, I used both routes that CJ described, and both result when done right, in more than 80% yield even!
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Corrosive Joeseph
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| Quote: Originally posted by nimgoldman | Second method uses the Leuckart amination (using formamide). The researchers didn't use a Kugelrorh for workup and the GC-MS spectra still looked very
good.
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These guys copied the errors straight from the MDA synthesis in M.V. Smith's 'Psychedelic Chemistry', which was in turn copied from Chemical Abstracts
52, 11965 (1958), let me know what happens when you stir your formyl-amphetamine with H2O2............ It should read H2O.
They don't give any yields either (facepalm)
/CJ
[Edited on 17-3-2019 by Corrosive Joeseph]
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nimgoldman
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Yes I am surprised I found the procedure in "Psychedelic Chemistry" from Smith. I have it printed but I never thought it is there... it is under
"Mescaline and friends" chapter - I would never look for it there.
| Quote: Originally posted by Corrosive Joeseph | Will you do me a favour and keep it here please. In my opinion, you have two real options.........
(1) Iron and acid to the ketone, steam it out, vacuum distill, zinc-nickel-NH3 to the primary amine.
(2) NaBH4-CuCl2 one-pot
You can thank me later.
/CJ
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Sure no problem.
(1) Can you please elaborate on "zinc-nickel-NH3 to the primary amine" ?
(2) I tried NaBH4-NiCl but that turned up as failure, but I might as well made some mistake in the workup.
I still have about 5 grams of very pure nitropropene, so I will decide on the reduction after I am sure the method actually works, at least for some
people. I am suprised how many writeups and even methods published in academic journals turn out not actually working ... especially about a reaction
that is extremely common in clandestine laboratories.
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TheMasterOfTheInternet
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NiCl2+NaBH4 and Ra-Ni+NaBH4 both have a slightly tricky workup and if the reaction time was too short I ended up with the solid colorless oxime (I
think) instead of the amine. Also I think the reaction is extremly sensitive towards inpurities in the educt.
Decolorisation (hydrogenation of the double bond) is very fast in this reaction but reduction of the -NO2 to -NH2 is slow, so this might be also a
reason why many failed it (looks like it's finished when it's not even the half way through the reduction).
After several failures got yield around 55% for the harder ones (which also won't work with most other methods) and reproducable 80-90%(!) for the
more usual simpler educts. The most important trick is to avoid A/B extraction*. An Ra-Ni is better than NiCl2/NiB but it works aswell. I haven't
tried copper chloride yet.
*For better workup:
I recommend first filtering the catalyst (can be reused several times btw.), wash catalyst with alcohol, add enough saturated potassium
carbonate solution to salt out an amine/alcohol layer, seperate phases, distill the alcohol off, then directly water-jet-vacuum-distill the clear
colorless product.
That's very much faster, cheaper, much safer and higher yielding than usual workup with B/A/B and especially simple A/B, which is a pain in the ass
with such a huge amount of NaBH4 and nickel in the reaction mixture (NaBH4 and acids can cause explosive reactions, Ni will form unfilterable slime
containing most of your product)
I also used a different procedure than ChemiPharma
On a-alkyl nitroarenes I added the educt first to an ethanolic NaBH4-solution (huge excess) slowly spatula by spatula, always waiting for
discoloration before the next spoon is added, keeping then temperature below 20°C with ice/water cooling to avoid dimeric byproducts. THEN I slowly
added the seperatly prepared catalyst in MeOH (NiB) or EtOH (Ra-Ni). Always got ~60-75% with NiB and easily 80-90% with Ra-Ni (I recommend W7- or T4
type as they're easy to make on your own and very active) on alpha-alkyl nitroarenes, but much less yield in the 35-65% range with nitroethenes,
unless adding tons of silical gel and the catalyst before, then I got 55~70% aswell, but that's different topic
[Edited on 18-3-2019 by TheMasterOfTheInternet]
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Chemi Pharma
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| Quote: Originally posted by nimgoldman | I just tried the NaBH4/NiCl2 procedure that Chemi Pharma proposed few posts back, but it didn't worked.
I followed the procedure to the letter and everything worked perfectly, even the smell of amine was very distinctive and I already though I have the
desired propanamine. Well, I didn't.
The product simply refused to precipitate. I tried pulling it in dry acetone, then crash it out with conc. sulfuric acid - no result. Then I tried HCl
- no result. I tried pulling it in IPA and add sulfuric - no result. I tried adding hexane to lower solubility but it only pushed everying into
separate aqueous layer.
I was desperate and even tried IPA + ether which produced some clouding that quickly disappeared. I managed to make white precipitate in one test
tube, but that ether was impure and I had to distill it first.
Meanwhile I placed the product in the freezer and when I finally had my ether, I pulled the product in IPA and added ether... and no reaction again.
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Yeah man, I got frustrated like you when I tried this kind of reaction a lot of times at the University Lab. I feel I wasn't completely honesty with
you guys about the study I've brought in my last threads. Alhough the smell of amine is preponderant, I had the same problems @nimgoldman had,
following the recipe. At the end of the work up I got just a few crystals that were filtered and had gave positive result to amphetamine, giving a
deep orange color with some efervecence with Marquis Reagent.
I tried to ajust the work up, first doing an B/A/B work up, instead A/B/A, like I just have said in my last threads, cause the dark red resine formed
while you put acid into the residue of the reaction (no matter if it was diluted HCL, ACOH or H2SO4, and I feel @TheMasterOfTheInternet is right when
he say Nickel hates acid media) after strip off the solvent (MEOH), because always some NIB pass trough the filter paper, and you end up with a black
sludge at the final of destilling MEOH.
Although I never tried or pay attencion to what @TheMasterOfTheInternet said in his last post, I think he is right talking about the tips and tricks
you have to pay attencion while doing this kind of reaction, mainly about the reaction time and the need of mantain the reaction temperature near to
0ºC, to avoiding polimerizated byproducts.
I remember that after follow the recipe I brought, in the part relative with the P2NP reduction, I had extended the time of the reaction, although
following the quantity of reagents and the order of adding it into the reaction flask.
First I did the methanolic NICl2 solution and put the indicated amount of NaBH4, turning the solution into a black color one. Next I added the P2NP at
once and extended the time of stirring to half an hour. Then I added the last required quantity of NaBH4 in very little quantities at a time to avoid
frothing, always mantaining the becker inside an ice bath. After all have been added, I still have stirred the reaction one more hour, to guarranty
total reduction of the NO2 group.
Its like @TheMasterOfTheInternet have said. The double bond is quickly reduced by alcoholic solution of NaBH4, no matter if you use MeOH, EtOH or
IPrOH. I'm trying yet to understand the role this three kind of alcohol does at the reaction, talking about the yields. On the other hand, the NO2
group is reduced to NH2 very slowly. First to oxime and then to amine and you have to use huge amounts of NaBH4 into alcoholic media with NIB (or may
be CuCl2 - I will try it yet) to do that as a second step, besides stand up the time of reaction.
Another thing I repute interesting in what @TheMasterOfTheInternet have said is about to avoiding the use of A/B or B/A work up and about the losses,
mainly using DCM in the work up. I don't know why, but I think he's right. DCM for some reason seems to screw up all the yield at the work up. May be
EtOAc could be better.
The idea of vaccum distilling the reaction mixture after distilling off the solvent seems to mee a good idea, and I will try this in my personnal lab
when I have a chance.
Good to see we are, all of us, evoluting here in this topic, switching experiences and knowledge, trying to solve a problem that became not solved for
the last 100 years, like @C/J said. And remembering @C/J, let's try to keep in this thread all discussion about alkyl nitrostyrenes synthesis and
reduction to aryl alkylamines, to facilitate the forum research in the future.
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TheMasterOfTheInternet
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I can easily tell you the difference between MeOH, EtOH and IPA, I've used them all for NaBH4 reductions.
NaBH4 has a high soloubility in MeOH but is very unstable in this solvent, so it's not useful for long reaction
times or you have to add it continously or as late as possible or several times the amount of NaBH4 than you would need than in EtOH or IPA. But also
reaction times seem to the fastest in MeOH
NaBH4 is quite stable in IPA, but has a very low soloubitly in it - you would need much more solvent OR you're getting a higher
tendency towards dimeric byproducts, as if the NaBH4 isn't fully dissolved there's never such an high excess of it available than in EtOH or MeOH. IPA
works but it's inferior to MeOH and EtOH, as it has longer reaction times and product is less clean. Also most salts are insolouble in this solvent so
you can't produce NiB or CuB in-situ. I don't recommend this solvent for most NaBH4 reductions. Another benifit is that the workup is
easier, as you can salt-out it much easier than MeOH and EtOH (no K2CO3 necessary, sodium chlorid solution is good enough).
EtOH is in the middle between them and usually the solvent I recommend for NaBH4 reductions. It don't has to be dry
99% EtOH, usual azeotropic 94-96% with a little MEK works well too. Nickel acetate has quite a low soloubilty in this solvent, that's why I don't
prepare the NiB-catalyst in situ when using this solvent. Though NiCl2 dissolves quite good. It don't know which copper salts could be used.
And I don't think 0°C are necessary, it would only lower the reaction times and soloubility of NaBH4 - 10-20°C works perfectly well for
alpha-alky-nitroarenes and gives best yields.
After complete discoloration much higher temperatures (refluxing) are no problem.
[Edited on 19-3-2019 by TheMasterOfTheInternet]
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